Heterocyclic phosphorus compounds

ABSTRACT

A heterocyclic phosphorus mono-, di- or polyester has the constitution of the product prepared by reacting an intermediate of specified type with a di- or polyol or derivative thereof capable of yielding the di- or polyol on hydrolysis, said intermediate of specified type being a heterocyclic phosphorus compound having the constitution of the compound prepared by reacting an olefin polymer or copolymer having at least 50 carbon atoms and containing olefinic unsaturation with a phosphorus trihalide in the presence of a Friedel-Crafts catalyst, preferably consisting of an aluminium halide, to form a reaction product having halogen atoms attached to phosphorus, and thereafter reacting the reaction product with a hydroxy compound, preferably water or methanol, to remove one or both of the halogen atoms attached to the phosphorus atom. Lubricating compositions containing the mono-, di- or polyesters of the invention are also described.

[ June 24, 1975 HETEROCYCLIC PHOSPHORUS COMPOUNDS {75] inventors: John Scotchiord Elliott; Bryan Terence Davis; Monty Frederick Crook, all of London, England [73] Assignee: Edwin Cooper & Company Limited,

London, England 122 Filed: Feb. 13, 1973 21 Appl. No.: 332,125

[30] Foreign Application Priority Data Feb. 18, 1972 United Kingdom 7582/72 [52] US. Cl 260/927 R; 252/489; 260/403; 260/502.4 R; 260/543 P; 260/920; 260/936 [5 1] Int. Cl. C07F 9/32 [58] Field of Search 260/920, 927 R, 936, 968, 260/978 [56] References Cited UNlTED STATES PATENTS 2,974,l58 3/l96l Lanham 260/927 R 3,092,650 6/1963 McBride ct al 260/978 X 3,729,532 4/l973 Jungermann et al. 260/936 Primary Examiner-Richard L. Raymond Attorney, Agent, or FirmBacon & Thomas 5 7 ABSTRACT A heterocyclic phosphorus mono-, dior polyester has the constitution of the product prepared by reacting an intermediate of specified type with a dior polyol or derivative thereof capable of yielding the dior polyol on hydrolysis, said intermediate of specified type being a heterocyclic phosphorus compound having the constitution of the compound prepared by reacting an olefin polymer or copolymer having at least 50 carbon atoms and containing olefinic unsaturation with a phosphorus trihalide in the presence of a Friedel-Crafts catalyst, preferably consisting of an aluminium halide, to form a reaction product having halogen atoms attached to phosphorus, and thereafter reacting the reaction product with a hydroxy compound, preferably water or methanol, to remove one or both of the halogen atoms attached to the phosphorus atom. Lubricating compositions containing the mono-, dior polyesters of the invention are also described.

5 Claims, No Drawings HETEROCYCLIC PHOSPHORUS COMPOUNDS The present invention relates to heterocyclic phosphorus mono-. dior polyesters which are particularly useful as lubricating oil additives.

In our copending United States Application Ser. No. 263,450 filed [6th June 1972, now abandoned, there is described an intermediate which is described as a heterocyclic phosphorus compound having the constitution of the compound prepared by reacting an olefin polymer or copolymer having at least 50 carbon atoms and containing olefinic unsaturation with a phosphorus trihalide in the presence of a Friedel-Crafts catalyst, preferably consisting of an aluminium halide, to form a reaction product having halogen atoms attached to phosphorus, and thereafter reacting the reaction product with a hydroxy compound, preferably water or methanol, to remove one or both of the halogen atoms attached to the phosphorus atom. Such intermediates will hereinafter in this specification and the claims appended hereto be referred to as an intermediate of the type described.

According to the present invention there is provided a heterocyclic phosphorus mono-, dior polyester having the constitution of the product prepared by reacting an intermediate of the type described with a dior polyol or derivative thereof capable of yielding the dior polyol on hydrolysis.

It is preferred to react the dior polyol or derivative thereof with the intermediate of the type described wherein both halogen atoms have been replaced.

Preferred dior polyols for use in the present invention are compounds having the following general formula:

ca oa l O (I ca oa CHZOH i R" and R" are the same or different and each is a hydrogen atom, an alkyl group, preferably a methyl or ethyl group, or an alkylol group, preferably a methylol group; R"" is an alkylene group, preferably an ethylene or propylene group; v is zero or an integer, preferably an integer of from 1 to 10; and the combination of R, R" and R is such that the compound contains at least two hydroxyl groups. Derivatives of such dior polyols which may usefully be employed include the monoethers, oxides, oxetanes and carbonates thereof.

Examples of suitable dior polyols which may be used include glycols, such as ethylene, propylene, bu-

wherein R, is an alkyl group, preferably a methyl or ethyl group or an alkylol group, preferably methylol, or the group O C CH OH CH OH notable examples of such polyols being trimethylol propane and pentaerythritol.

It is particularly preferred to use oxetanes or carbonates derived from the aforementioned polyols.

In a further aspect of the invention the reaction product of the intermediate of the type described and a dior polyol or derivative thereof my be further reacted with a dicarboxylic acid or derivative thereof, for example, an anhydride or lower alkyl ester thereof which is capable of reacting to form the required ester.

Examples of suitable dicarboxylic acids include sebacic, azelaic, adkpic, glutaric, maleic and succinic acids and alkyl and alkenyl succinic acids, e.g. dodecenyl and polybutenyl succinic acids. Alternatively the so-called Dimer acids, obtainable by the dimerisation of unsaturated fatty acids such as linoleic acid, may be employed. In general these acids may be described as having the formula:

HOOC R COOH wherein R is an alkylene, hydrocarbon substituted alkylene, arylene, alkarylene or aralkylene radical. Preferably R is a saturated or unsaturated, straight or branched chain alkylene radical containing from 2 to 200 carbon atoms, possibly including in its structure a saturated or unsaturated ring.

The mono-, dior polyesters which are the subject of this invention are difficult to characterise and will invariably consist of mixtures of products having the general empirical formula:

A"! il DP wherein each A is the same or different and is believed to have the structure,

each B is the same or different and has the formula each D is the same or different and has the formula -OCR-CO-;

m and n are integers of from 1 to and p is zero or an integer of from l to 20. In each group B:

x is zero or an integer of from 1 to 7;

y is an integer of from 1 to 8; and

(x y) is an integer of from 2 to 8. For the molecule as a whole:

n x is preferably at least l, more preferably at least 2; and

The groups A, B and D may be linked together in one of the following ways: AB, ABA, ABDB, ABDBA, ABDBDBA,

LmLeA, Aer: etc. etc.

I l A D etc. wherein it is understood that the values of x and y are chosen such that there are no free valencies and wherein R is as defined above; R and R are the same or different and are straight or branched chain hydrocarbon groups, at least one containing at least 20 and preferably at least 30 carbon atoms, R more preferably being hydrogen, methyl or ethyl and R more preferably containing at least 40 carbon atoms; R R and R are the same or different and may be hydrogen or hydrocarbon, preferably hydrogen, methyl or ethyl; R is hydrogen or methyl; and R is an alkylene, oxyalkylene or polyoxyalkylene group. The groups R R R R R and R are usually derived from polypropylene or polyisobutylene having a molecular weight of from 700 to 3500 and therefore usually contain collectively from 50 to 250 carbon atoms.

B is preferably derived from trimethylol propane or pentaerythritol.

The invention also includes a process for the preparation of heterocyclic phosphorus mono-, dior polyesters suitable as lubricating oil additives which process comprises reacting a compound of the formula:

wherein R R R R R and R are as hereinbefore defined and Y is a halogen atom or a hydroxyl group, preferably a hydroxyl group, with a dior polyol or derivative thereof as hereinbefore defined, and option ally, thereafter reacting the product with a dicarboxylic acid or derivative thereof and further dior polyol if desired, to form mono-. dior polyesters of the type he re inbefore described.

It is preferred to use a derivative such as the oxetane or carbonate ofa polyol or the oxide of a diol in carrying out the initial esterification.

The intermediate of the type described, believed to be a phosphinic acid or phosphinic acid halide of the above proposed general formula, and the dior polyol or derivative thereof may be reacted together at the highest temperature possible depending on the boiling point of the reactants but not so high as to degrade the hydrocarbon chain. Thus. temperatures much in excess of 260C should be avoided and the reaction is usually carried out at a temperature between l and 200C. However, when the lower alkylene oxides are used at atmospheric pressure, the temperature of the reaction will be ambient temperature or slightly below, i.e. from about 10C upward.

The reactants are heated together for sufficient time and at a sufficiently high temperature to give a reasonably low acidity, preferably less than 5mg KOH/g and it is desirable that the acidity should be less than 3mg KOH/g.

The esterification ofthese products with dicarboxylic acids is carried out under normal esterification conditions using small amounts of known esterification catalysts in a water carrying solvent such as benzene, toluene or xylene, the latter being preferred.

The acidity of these esters again should be as low as possible, preferably less than lOmg KOH/gm and more desirably less than 5mg KOH/g.

It is to be understood that in another aspect the invention provides a lubricating composition comprising a major amount of lubricating oil and a minor amount, e.g. from 0.1 to l0% by weight, based on the total weight of the lubricating composition, of a mono-, dior polyester as hereinbefore described.

There now follows by way of example typical preparations and compositions in accordance with the present invention, wherein amounts and proportions of phosphinic acid and phosphinic acid halide intermediates expressed as equivalents are equivalents based on phosphorus content.

EXAMPLE l To l33.2g 1 mole) of anhydrous aluminium trichloride, dissolved in ml methylene dichloride in a glass vessel cooled in an acetone/dry ice bath, were added over 10 mins. l37.6g (l mole) of phosphorus trichloride in 100 ml methylene dichloride. To this was added 840g (l mole) of polypropylene having a molecular weight of 840 dissolved in 500 ml of methylene dichloride over 35 minutes whilst maintaining the temperature below 8C and with continuous stirring. The reaction mixture was stirred for a further 3 hours at from 5 to l0C, a further 250 ml of methylene dichloride being added after 2 hours. 500 ml methanol were then added whilst maintaining the temperature below 15C. The temperature of the mixture was then allowed to rise to room temperature over one-half hour with continued stirring. The resultant solution was filtered through Speed flow filter-aid and the pad was then washed with methylene dichloride and commercial hexane of boiling range 62 68C (designated S.B.P. 62-68). The lower, methanol, layer of the filtrate was discarded and the upper layer washed with 500 ml of methanol/water 1:1 by volume). The lower layer now contained the product and this was stripped and steam hydrolysed for 12 hours on an oil bath at 160C. The product was dissolved in S.B.P. 6268, washed four times with 250 ml aliquot portions of methanol/H O 1:1 by volume) and stripped to a bath temperature of 175C/6mm. The product was filtered hot through "Speed plus filter-aid to yield 661g (73%) of a polypropylene phosphinic acid containing 2.45% P (calc 3.4371 This would amount to a 65% conversion of the polypropylene. This was confirmed by acidity and saponification value determination and by column chromatography using activated alumina.

138g (0.1 equivalents) of this product (designated Intermediate I hereinbelow) was placed in a 3 necked glass flask fitted with stirrer; nitrogen bleed and dropping funnel. 128g (0.] 1m) of trimethylol propane oxetane (3 ethyl 3 hydroxymethyl oxetane) was added at room temperature with stirring and the bath temperature raised to l80l 90C for 6 hours until the acidity of the product was reduced to 1.1mg KOH/g. the acidity of the starting material being 34.8mg KOH/g. The product was stripped under vacuum (2mm) to a bath temperature of 210C. then filtered at 100C through Speed plus. 125g of product (83% were obtained, containing 1.96% phosphorus (calc 2.06% Similar batches were prepared containing varying amounts of phosphorus and these were used in certain of the later Examples, being designated compound A" in each case.

The trimethylol propane oxetane employed in this Example was prepared from trimethylol propane (3.0 moles). diethyl carbonate (3.0 moles) and I pellet of NaOH by reaction at a bath temperature of 150C and thereafter removing excess diethyl carbonate (274g) by distillation and removing ethanol up to a still-head temperature of 80C. The residue was heated at a bath temperature of 240C under 40-50 mms Hg vacuum, yielding 296g (85%) mobile distillate as desired product.

EXAMPLE 2 A similar preparation was carried out using a large excess of trimcthylol propane instead of the oxetane used in the previous example. In this manner the acidity of the product was reduced to 33mg KOH/g after 45 hours. The acidity was further reduced to 1.4mg KOH/g after a further 7 hours reaction with a small quantity of trirnethylolpropane oxetane.

EXAMPLE 3 A similar preparation to that of Example 1 was carried out using 31.8g (0.024 equivalents) of the same intermediate phosphinic acid and 4.05g (0.025 mole) of pentaerythritol carbonate. an additional 2g of the carbonate being added during the course of the reaction. The acidity was reduced to 1.7mg KOH/g after 26 hours. The product was taken up in S.B.P. 62/68 and solvent was removed by stripping to a temperature of 185C under a pressure of 4mmHg. The product was filtered hot. [3.8g (43.5%) being obtained and was found to contain 2.18% P (Cale 2.13%). The pentaerythritol carbonate was prepared by transesterification of 68g (0.5 mole) of pentaerythritol with 59g (0.5 mole) diethyl carbonate in ml of dimethyl formamide in the presence ofa small amount of sodium hydroxide (0.5g approx.) 49.7g (calculated 46g) of ethanol were distilled off through a packed column during the reaction.

EXAMPLE 4 15g of an ester product similar to that obtained in Example and lg of maleic anhydride were refluxed in 10 ml xylene for 3 hours. A further 15g of the ester in 20 ml of xylene were then added and the xylene removed by distillation at atmospheric pressure. The material was then stripped under a vacuum of 280 mm at 190C bath temperature and filtered to yield 188g of a product containing 1.91%! (calc 2.02%

In certain cases other intermediates were used. These intermediates were prepared in substantially the same manner as that of Example l which is designated Intermediate 1.

Intermediate [1 Several preparations were carried out to form an acid chloride. The preparation was substantially the same as in Example 1 except for the work up procedure in which 500m1s of anhydrous methanol and 2 X 50mls aqueous methanol per mole of a commercially available polyisobutylene (PIB) having a molecular weight of 1000 were used. The batches were combined and the product steam hydrolysed for several hours, extracted with special boiling spirit 62/68, washed with 1:1 water/methanol and stripped under vacuum to about C. The product contained 1.63%P and 0.25%Cl.

Intermediate 111 This was derived from a commercially available polyisobutylene (PIB) of molecular weight 1300 (I950g, 1.5 moles), PCl (205g, 1.5 moles). AlCl (240g. 1.88 moles). These were reacted for 1 hour at a temperature of 5 to 10C in I500ml of dichloromethane. 800ml of dry methanol were added and a white precipitate filtered off and the methanol layer was discarded. The dichloromethane layer was washed twice with 500 ml of 1: l H O/methanoI, dried. filtered and steam hydro- Iysed for 14 hours.

The product was extracted with special boiling spirit, boiling point 62/68, washed with 500 mls 1:1 H O/methanol and stripped to 180C/5mm Hg. l390g (68%) of product was obtained and found to contain 1.0%P and 0.32%Cl.

The preparation of further compounds was carried out using a process substantially the same as in Examples l to 3. the amounts of starting materials and analysis of products being given in Table I wherein the refiltered. 1.6g of pentaerythritol being recovered. The 50 spective preparations are designated Examples 5 to 8.

TABLE Example Example Example Example 5 6 7 8 Intermediate |(ex.840rnw I(ex. 840mw |l(ex.1000mw I1I(ex.1300mw PIB) Polypropylene) Polypropylene) PIB) Equivalents (based on P) 0.05 0.1 0.075 ()4 Dior polyol or derivative Trimethylol propane Ethylene Trimethylol propane Trimethylol propane carbonate Oxide oxetanc oxetane weight (g) 2.2:: 9.56 46.5

TABLE I -Continued Example Example Example Example 200ml. moles 0.08 0.0825 0.4 solvent 100ml.

SBP 62/68 Temperature of Reaction "C 220-260 15-75 190-200 190-200 Time of Reaction (hours) 28 l4 17 20 Comments Small amounts of The ethylene oxide 3 portions of 2g. of

trimethylol propane was cooled to C oxetane added during oxetane added during and blown into the reaction. reaction to reduce reaction mixture acidity. with dry N .Solvent and used epoxide was recycled after being caught in a cold trap. Found 219 2.1 1.57 1.2 '%P Calc. 2.04 2.08 1.54 0,97 Acidity mg. KOH/g. 4.9 3.7 1.5 42 Yield Wt.(g) 51 102 138 1000 it 69 69 92 80 20 EXAMPLE 9 EXAMPLE l3 87.5g (0.06 equivalents) of a product similar to that of Example 1 (hereinafter designated compound A) and 17g (0.03m) Empol dimer acid were heated under nitrogen for 6 hours at 195C, after which time the residual acidity was 6.6mg KOH/g. Further reaction for a total of 32 hours at temperatures up to 225C failed to lower the acidity, despite the addition of and excess of the product similar to that of Example 1 at 17 and 26 hours. The product was filtered hot through Speed-plus, whereupon 93g (87%) was obtained which was found to contain 1.89%P (calc. 1.8).

EXAMPLE 10 This product was prepared in substantially the same manner as in Example 9, except that 98g (0.066 equivalents) of A and 17.5g (0.033m) of a polyisobutenyl succinic anhydride derived from a PlB of mw 425, were used in the reaction. The total reaction time was 35 hours. 5% and 10% ofA was added at 12 and 23 hours. 75g (83.5%) ofa product was obtained having an acid ity of 16.9mg KOH/g and containing 1.99%P (calc. 1.82).

EXAMPLE 1 l 75. lg (0.05 equivalents) ofA and 4.9g (0.5m) of maleic anhydride were refluxed in 60ml of xylene until the anhydride content (infrared analysis). residual acidity or water yield indicated sufficient reaction which took about 3 hours. 4.0g (0.03 moles) trimethylol propane and 0.2g of paratoluene sulphonic acid (PTSA) were then added and refluxed for a further 31 hours; two portions each of 0.3g (total excess) of trimethylol propane were added after 12 and 28 hours. The product was filtered, washed with 50m] 1:1 aqueous methano], separated, dried and stripped. The yield was 85% and the acidity 7.0mg KOH/g and the product was found to contain 1.94%P (calc. 1.88).

EXAMPLE 12 The reaction was carried out substantially the same as in Example 11 with the following parameters: 583g (0.04 equivalents) of A, 4g (0.04m) succinic anhydridc, 50ml xylene, 2.68g (0.02 mole) trimethylol pro pane and 0.2g PTSA added after 2 /2 hours and refluxed for a total of 20 hours, additional PTSA and solvent being added after 6 hours. Yield 657:, 7(P I 1.86 (Calc. 1.93), acidity 20mg KOH/g.

Substantially as in Example 1 l, with the following pa rameters: 75.1g (0.05 equivalents) of A. 7.3g (0.05

5 moles) adipic acid, 5.0m] xylene. 3.35g (0.025 moles) trimethylol propane and 0.2g PTSA added after 1 /2 hours. Total reflux time 30% hours. Additional PTSA and solvent added after 5%, l 1% and 18 hours. Yield %P (Calc. 1.81). Acidity 3.8mg KOH/g.

EXAMPLE 14 The reaction was carried out substantially as in Example l 1, with the following parameters: 605g (0.04 equivalents) of A and 40 g (0.04 moles) Empol 1014 dimer acid were refluxed for 1% hours and 268g (0.02 moles) oftrimethylol propane were added, the reaction being continued for a total of 25 /2 hours. Additional solvent and PTSA were added after 6%, 12% and 19 hours. Yield 81%, 76 1.56 (Calc. 1.45). Acidity 2.0mg KOH/g.

EXAMPLE 15 The reaction was carried out substantially as in Example 11, with the following parameters: l158g (0.36 equivalents) product of Example 8, 52.6g (0.36 moles) adipic acid and 1.2g PTSA were refluxed for 2% hours. 242g (0.18 moles) of trimethylol propane were added and refluxed for a further 9 hours. Yield 78%, %P 1.09% (Calc. 0.91). Acidity 3.8mg KOH/g.

EXAMPLE 16 EXAMPLE l7 144.8g (0.1 equivalents) of a product prepared in a similar manner to that of Example 3, 14.6g (0.1 moles) adipic acid and 03g PTSA were refluxed in xylene for 3V2 hours. 6.8g (0.05m) pentaerythritol were added and the mixture refluxed for 3 hours. The solvent was removed and the mixture heated at l90-200C for 6 hours. 2g pentaerythritol was added and the heating continued for a further 6 hours. Yield 79%. 7(P 2.02% (Cale. 1.90). Acidity 8.7mg KOH/g.

EXAMPLE l8 665g (0.05 equivalents) of Intermediate I were reacted by stirring at 200220C for 18 hours with a total of 0.6 moles (21.25g) of ms methyl diglycol orthoformate. previously prepared by transesterification of methyl diglycol with triethyl orthoformate. Stripping of the product yielded a residue of 58g (81% yield /ZP 2.24 (Cale. 2.l6). Acidity 5.8mg KOH/g.

The tests were carried out in a slightly modified form of the normal apparatus. Instead of continuous oil splashing, the oil was splashed against the aluminium panel maintained at 600F for 3% hours using a timing device to give a l second splash and 45 second period when the paddle was stationary. The apparatus was further modified to allow a flow of moist air through the sump above the oil surface at the rate of 2.3 litres per hour.

The weight change and appearance of the panels were observed after test, the appearance of the panels being assigned merit ratings which were determined by comparing with a set of 28 panels divided into four groups. Where the panels were merely stained these EXAMPLE l9 panels were given numbers l 7 in increasing order of staining, i.e. number 1 was practically clean and num- 66.5g (0.05 equivalents) of Intermediate 1 were ber 7 was black, the number being followed by the sufacted at 200-240C for 29 hours i h 2 portions f fix 0" indicating "ordinary" staining. In the second l5.4g (0.055 moles) of dipentaerythritol carbonate" 20 g p the Same numbers r igne 1 7 but the [previously prepared by transesterification of dipenta- Suffix was PlflCed after the number 10 mdlcale that erythritol (0.25 moles) with diethyl carbonate (0.25 It had the same staining but was lacquered stmlhtrly m moles) in dimethyl formamide solution and catalysed group 3 the Sum) Showed the appearancfi of by one pellet of NaOH, with the removal of 16.4g of hieS on the same bflekgreuhd- In group the Sutfix th l], Th idi d d to 13 KOH/ d was 25 showed that the panel was sooted, the number referring lowered to 7mg KOH/ b ti at 200L240C i h to the panel colour. A rating of 4 0 or less was consid- 3g of trimethylol propane oxetane. The product was filered to reasonable- I tered in S.B.P. 62/68 solution, stripped and filtered at In addltleh t0 the foregoing rating of the l the IOOOC through a finer an Yield 51g (65%) c p area of the sump not normally immersed ln oll was 2 17 C l 93 i i 1 lomg 0 30 rated according to the percentage cleanliness in much Th ff ti f h above products was demon the same manner as an engine piston is rated after a test rated by dissolving 35% by weight of the above such as the Caterpillar l-G test. It is believed that the mentioned Compounds in place of the dispel-Sam in a above-mentioned test correlates well with the Caterpilfully formulated MIL L 2lO4C formulation and G Engme TeSt- I testing the formulation so prepared in the well known 35 It nollcedthat m g l f the Products of the "Panel Coker Test. The results ofthese tests are given prelsem mvemlon Improved p in Table rating over the prior art products.

TABLE II Sump Panel Example Merit No Dispersant Rating Rating Wt. Gain( mg) 20 Product of Example I. 94.6 1-0 l0 2l (4 different batches) 88.0 3-0* 28 22 87.5 3-0 [4 23 88.5 3-0 9 24 Product of Example 2. 85 3-0 15 25 Product of Example 3. 78.5 4-0 I7 26 Product of Example 5. 92.2 4-0 [9 27 Product of Example 6. 74.8 3-0 I2 28 Product of Example 7. 88.5 3-0 12 29 Product of Example 8. 90.2 3-0 20 30 Product of Example 9. 88.0 3-0 13 IN Product of Example [0. 89.3 3-0* 20 32 Product of Example I i. 83.7 3-0 [5 33 Product of Example [2. 88.0 3-0 [8 34 Product of Example [3. 88.0 3-0* 22 35 Product of Example l4. 83.3 3-0 23 36 Product of Example l5. 87.3 2-0 5 37 Product of Example l6. 90.2 3-0 I4 38 Product of Example [7. 87.5 3-0 l4 39 Product of Example l8. 94.9 3-0* l5 40 Product of Example l). 93.] 3-0 l7 Commercially available Mannich 74.5 3-0 29 base derived from l900mw PlB used in 5.4% concentration. 605 3-0 l2 Commercially available ester 68 3-0 35 of a polyisobutenyl succinic acid derived from l000mw PIB 78 3-0 l8 and pentaerythritol.

PlB substituted phenol}formaldehyde/pulyamine condensation product. lndicates a hand of lacquer.

We claim: I. A heterocyclic phosphorus monoor polyester product prepared by reacting a polyol of the formula:

- C CH OH CH OH CH,OH

I CH UH R" and R"' are the same or different and each is selected from the group consisting of hydrogen, methyl, ethyl and methylol, and the combination of R, R" and R' is such that at least two hydroxyl groups are presem; or a monoether, oxide. oxetane or carbonate which yields said polyol on hydrolysis; with a heterocyclic phosphorus compound prepared by reacting an olefin polymer or copolymer having a molecular weight in the range of about 700 to 3500 and containing olefinic unsaturation with a phosphorus trihalide in the presence of a Friedel-Crafts catalyst to form a reaction product having hydrocarbon and halogen attached to phosphorus. and thereafter reacting the reaction product with water or methanol to remove one or both of the halogen atoms from the phosphorus atom.

2. The monoor polyester product ofclaim I wherein both halogen atoms are removed from the heterocyclic phosphorus compound before reaction with said polyol.

3. The monoor polyester product of claim 1 wherein the olefin reactant is polypropylene or polyisobutylene.

4. An ester according to claim I wherein the polyol is selected from the group consisting of ethylene, propylene, butylene, neopentyl, polyoxyethylene and polyoxypropylene glycols.

5. An ester according to claim I wherein the polyol is a compound having the general formula:

ca 0a l R C CH OH I CH2OH wherein R is selected from the group consisting of methyl. ethyl, methylol and the group ca oa o c ca oa CH OH 

1. A HETEROCYCLIC PHOSPHOROUS MONO- OR POLYESTER PRODUCT PREPARED BY REACTING A POLYOL OF THE FORMULA:
 2. The mono- or polyester product of claim 1 wherein both halogen atoms are removed from the heterocyclic phosphorus compound before reaction with said polyol.
 3. The mono- or polyester product of claim 1 wherein the olefin reactant is polypropylene or polyisobutylene.
 4. An ester according to claim 1 wherein the polyol is selected from the group consisting of ethylene, propylene, butylene, neopentyl, polyoxyethylene and polyoxypropylene glycols.
 5. An ester according to claim 1 wherein the polyol is a compound having the general formula: 